Amino-thiophosphoric acid esters and a process for their production



PROCESS FOR THEIR PRODUCTION Gerhard Schrader, Wuppertal-Cronenberg, Germany, as

signor to Farbenlabriken Bayer Aktienge sellschaft,

Leverkusen, Germany, a corporation of Germany No Drawing. Filed July 31, 1959, Ser. No. 830,740 Claims priority, application Germany Aug. 20, 1958 6 Claims. (Cl. 260-461) ier The present invention relates to and has as its objects" new and useful insecticidal amino-phosphoric acid esters and a process for their production.

Generally these compounds may be represented by the following formula lower yl 'fi/O-lower alkyl lower alkyl S-R A in which R stands for phenyl-lower alkyl, cyano-lower alkyl, dialkyl-amino-lower alkyl, or lower carbo-alkoxyi carbonyl-lower alkyl. i

It is already known to produce certain amino-phos phoric acid-O-alkyl-S-alkylmercapto-alkyl esters by re-; acting corresponding amino-phosphoric acid ester chlo- {.14 wi h, .alkyl-me capt zalkyl ere pta s. his 'r a air-(Hammer "of compounds 'o'fthis kind'are fdescribe d in United States PatentNo..2,,8 8vl,20l; Lower "dialkyl-amino-phbsphori'c "'zicid O-alkM-S-za'lkyl esters in which the S-alkyl-gropp'is substituted as shown above are not yet known froiniithe literature. These new compounds-are found to be insecticidal compounds with outstandii g properties! A very economi process has also been found for obtaining 'thQSeamino-phosphoric acid-O-alkyI-S alkyl esters. This process consists, starting from amino-thionophosphoric acid dichlorides which are obtainable from phos- (C Ha) zN-P The last mentioned salt or corresponding compounds thereto may be reacted as described above with suitably substituted alkyl halidesto yield the inventive co'ihpoii nd'sl The new 'di- (low'ef-alkyl )famino thiolphosphoric acid esters described in thisinvention are distinguished by a good insecticidal action. The"; application of the com- +Nacl as,

pounds takes place in a manner known in principle prefer- 5,; ably by mixing the resulting active substances with a dissolving assistant such as *e.g. acetone or dimethyl formamide andsfurtheiifmiiring'l' witlr 'a'i commercially usual emulsifier preferably of-a-noneiqnic type based on an .aryl hydroxy polyglyoofetlier. fIlie'pr'eliminary mixtpre "isthe'n diluted with watertonhe desired active-concen- Spider mites are killed to the Xteht tained as a weakly yellow water-insoluble oil.

. tratiommApplication is however likewise often desirable AMINO-THIOPHOSPHORIC ACID ESTERS t.

in powder form iwhereby the compounds according to the present invention are mixed with suitable solid extenders,

: The following examples give a summary of the new process and the 'new compounds.

Example 1 O Cz Hi 48 grams (0.25 mol) of dimethylamino-thionophosphonic acid-ethyl-ester chloride (B.P. at 60". ,mm, Hg) are dissolved in 130 ml. of anhydrous alcohol. '30 ml. of water are added thereto andsubsequently a solution of 29 grams of potassium hydroxide .in 60 ml. of water. is heated to 60-70" C. for 2 further hours and 33 grams (0.25 mol) of benzyl chloride are 'added with stirring. The reaction product is'hel'd with stirring at 70 C. for a further two hours. Sodium chloride separates. The reaction product is then diluted with 300 ml. of benzeneand these shaken out in a separating funnel with 100 ml. of water. After separation and drying the benzene solution with sodium sulfate the: filtrate is fractionated. 32 grams of the new ester are obtained as-,a "colorless water-insoluble oil of B.P. 8 '9" G 0.01 mm. Hg. Yield 50% ofthe theoretical. On rats per os the product fp'ossesses 'a medium toxicity of 100 lug/kg.

. f wwith At 0.01% concentrations thdester 0.1% solutions.

shows 100% systemic action against aphids."

r- ExaritpleZ r 48 grams (0.25 mol) ofdimethylamino-thionophosphoric acid-ethyl ester. chloride are dissolved as in Example 1 in 130 m1. of alcohol and 30 ml. of water. 'Hydrolysis is then carriedou't' with 29 grams of potassium hydroxide in: 60 ml. of .water. To.the resultingsolutioil arguing (0.25 mol) of p-cmem-benzyrmmaae are the dimethyl-amino-thiolphosphoric acid-O-ethyl ester added with stirring at 60 C. The temperature is held at 70'C. for a further 2 hours and working up follows as in Example 1. 45 grams of the new ester are ob- Yield 61% of the theoretical. .The compound may not be distilled Without decomposition even in high vacuum.

.water.. .Ifo the r.esulting,,.solution .35.gramsmflllimql) of fi-chloro-propionitrile is added with stirring. l-lea tihg is continued at 70 C. for-afurtherZ hours and working up is carried out in the usual way. 20 grams oflthe new ester are obtained as a weakly yellow insoluble oil of boiling point C./0'.01"mm. Hg. Yield 36% of the theoretical.

Rats per os LD 25 mg. /kg.'- Aphids and spider mites are killed to the extent of "with 0.1% solution. The preparation has outstanding ovicidal action on the eg'gsof thered spider.

' I In a corresponding manner the following compounds are produced:

- apnoea in which R stands for a member selected from thetgr'oup 2381 3:01

o rats per os Compound B.P. yield, medium percent toxicity, mg/kg.

calms-P 0.01mm./75.. Y 2.5

S-CH:CH:-N(C:Hs):

O OCIH (CH1) :N-P not dis '7 1 ,000

SGnHa o 0.0mtbmnN-r 3 0.01 mm./73.-.- so 500 s-c'm-ooomm "(Cfiz)zN"-=P 0.01 mm./74.-.; 51 100 Y CH: fi/OCzH; '(CH;);NP\ 0.01 aim 68"; 62 250 To determine the special utility the compounds shown lower alkyl, and'w'herein lower an -yr stands for an alkyl in the table below were tested as to the activity against radical up to 4 carbon :atoms. I aphids and spider .mites. Aqueous solutions of these .2. The compound'dfft'he following formula compounds have been prepared .by mixing the active ingredient with the (same amount of dimet'hyl formarnide as an auxiliary solvent adding thereto 20% by weight (=C'H5)zN-P referred to active ingredient of a commercial emulsifier Q consisting of a benzyl hydroXy polyglycol ether containing about 10 to 15 glycol residues,and diluting this prea a V V J 4 1 A mixture at last with water to the desired concentration The compound of the 'fonowmg formula indicated in the table below. 40 7 go 0 Cam The aphidtests were carried out In the known manner y v p with the species Aphis fabae on Vitia faba by spraying v the infested plants with the active emulsion until drip S-CHQ-Cl wet with evaluation after 2 or 4 days by counting'the deadpests either on the surface of the so l or still rc- Thefpcompound of the following f l mammg -on the plants. a

The fspider mite tests were carried 'out .in the known f0 oominann'er with the species Tetranychus alzae Hanst. on Q Phaseolus vulgaris by spraying the infested :plants with l the active emulsion until drip wet with evaluation after 24 hours, 48 hours and 8 days. l

The determination of the systemic action against aphids The compound of the followmg formula -was likewise carried out with Aphis fabae on Vitia faba, O 0 C H whereby the active emulsion was poured onto plants a 5 which had been planted in flower pots. (CHahN-P The following results were obtained: SCH,G00C,H5

aphids 0.01%- (CHa)2N-P {systemieactionon- 0.

aphids. SCHi-CHr-N(OzH )l 0 00B hd 0.1 7.. 1007 2 gid er mitess & 50%? (0H,),N-P spider mites ovlclda action.

systemicactionon 10.1%.. 00%- 'SCH3CH'1-'CN aphids.

I claim: '6. The compound of the following formula a Amino-thiolphospho'ric acidesters of the following o 00,3. formula (kcmymip lower alkyl '0 0lower alkyl 70 O I I NJ CH1 low galkyl m Referencesflitedfinthexfile' of this;patent 

1. AMINO-THIOPLHOSPHORIC ACID ESTERS OF THE FOLLOWING FORMULA 